U.S. patent number 6,906,218 [Application Number 10/322,273] was granted by the patent office on 2005-06-14 for cyclohexane derivatives and methods for their preparation.
This patent grant is currently assigned to Invista North America S.a.r.l.. Invention is credited to Alan M. Allgeier, Christian P. Lenges.
United States Patent |
6,906,218 |
Allgeier , et al. |
June 14, 2005 |
Cyclohexane derivatives and methods for their preparation
Abstract
Disclosed herein are methods for preparing nitrile derivatives
and their corresponding amines from 1-,2-,4-trivinylcyclohexane by
hydrocyanation, followed by hydrogenation. Also disclosed are novel
compounds used in the methods described herein.
Inventors: |
Allgeier; Alan M. (Wilmington,
DE), Lenges; Christian P. (Wilmington, DE) |
Assignee: |
Invista North America S.a.r.l.
(Wilmington, DE)
|
Family
ID: |
32592978 |
Appl.
No.: |
10/322,273 |
Filed: |
December 18, 2002 |
Current U.S.
Class: |
558/430 |
Current CPC
Class: |
C07C
255/31 (20130101); C07F 9/145 (20130101); C07F
9/65744 (20130101); C07C 2601/14 (20170501) |
Current International
Class: |
C07C
255/00 (20060101); C07C 255/31 (20060101); C07F
9/6574 (20060101); C07F 9/145 (20060101); C07F
9/00 (20060101); C07C 255/03 () |
Field of
Search: |
;558/430 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
DN 124:260012, DN DN 114:62379. .
DN 122:187242, DN89:163108. .
DN 121:280954. .
DN 121:133236. .
Suh et al.,Facile Syntheses of cis-Fused Carbobicycles via
Combination of Ciafsen Rearrangement of Macrolactone and Nitrile
Oxide Cycloaddition, Chemistry Letters, pp. 63-66, 1994. .
Int'l Search Report for PCT/US03/40247, May 27, 2004. .
Rienaecker, Brennstoff. Chemie, vol. 45, p. 206 (1964)..
|
Primary Examiner: Wilson; James O.
Assistant Examiner: Sackey; Ebenezer
Claims
What is claimed:
1. A compound of formula (I-A): ##STR47## wherein substituents on
the cyclohexane ring are in the 1-, 2-, and 4-positions, and
wherein Z is a --CH.sub.2 CH.sub.2 -- group or a ##STR48## group,
and n is an integer of 1 to 3.
2. A method for preparing the compound of claim 1 comprising:
contacting 1,2,4-trivinylcyclohexane with hydrogen cyanide, in the
presence of a catalyst, said catalyst comprising an organic
phosphorous ligand and a Group VIII metal, wherein said contacting
is done at a temperature of from about -25.degree. C. to about
200.degree. C.
3. The method of claim 2 wherein said contacting is done in the
presence of a Lewis acid promoter.
4. The method of claim 2 or 3 wherein said contacting is done in
the presence of a solvent.
5. The compound of claim 1 consisting of formula XXXVL:
##STR49##
6. The compound of claim 5 consisting of any of the formulae XXXVII
to XLII: ##STR50## ##STR51##
7. A composition, comprising two or more compounds of any two or
more of formulae XXXVII to XLII of claim 6.
8. The compound of claim 1 consisting of formula XLIII:
##STR52##
9. The compound of claim 8 consisting of any of the formulae XLIV
to LV: ##STR53## ##STR54## ##STR55##
10. A composition comprising two or more compounds of any two or
more of formulae XLIV to LV of claim 9.
11. The compound of claim 1 consisting of formula LVI:
##STR56##
12. The compound of claim 11 consisting of any of the formulae LVII
to LXIV: ##STR57## ##STR58##
13. A composition comprising two or more compounds of any two or
more of formulae LVII to LXIV of claim 12.
14. A composition comprising two or more compounds of formula I-A
of claim 1.
Description
FIELD OF THE INVENTION
The present invention discloses novel organonitrile and organoamine
compounds and methods for making them comprising hydrocyanation and
hydrogenation reactions, respectively. Specifically, disclosed are
cyclohexane derivatives containing nitrile groups and cyclohexane
derivatives containing amine groups.
BACKGROUND OF THE INVENTION
Cyclohexane derivatives containing nitrile groups are of great
interest as precursors to a variety of useful molecules with
applications as monomers for the production of polymers, or as
fragrance intermediates.
1,2,4-trivinylcyclohexane, which is used as a starting material in
the method according to the present invention, can be obtained, for
example, according to Rienaecker, Brennstoff-Chemie, Vol. 45, p.
206 (1964), by pyrolysis of 1,5,9-cyclododecatriene.
Prior to the present invention, it was not known that
trivinylcyclohexane could be converted to cyclohexane derivatives
with nitrile groups by employing a hydrocyanation process. It was
also not known that the so formed cyclohexane derivatives
containing nitrile groups could be converted selectively in a
hydrogenation process to the cyclohexane derivatives with the
corresponding amine groups. There is a need to access
cycloaliphatic hydrocarbons, which have one or more functional
groups, such as nitriles, amines, alcohols or carboxylic acids.
Especially cycloaliphatic hydrocarbons with two and more than two
functional groups are of interest.
Thus, there is a need for cyclohexane derivatives, which contain
nitrile groups. There also remains a need for a method to produce
cyclohexane derivatives, which contain nitrile groups. There is a
need for cyclohexane derivatives, which contain amine groups. There
remains also a need for a method to produce cyclohexane
derivatives, which contain amine groups. These needs are met by the
present invention.
SUMMARY OF THE INVENTION
The present invention provides for a composition of matter for
cyclohexane derivatives, said composition comprising a cyclohexane
derivative of the formula (I-A) having nitrile groups: ##STR1##
wherein (I-A) is alone or in combination with isomers thereof, and
wherein substituents on the cyclohexane ring are in the 1-, 2-, and
4-positions, and wherein Z is a --CH.sub.2 CH.sub.2 -- group or a:
##STR2##
group, and n is an integer of 1 to 3.
The present invention provides also for a method for preparing a
compound of the formula (I-A): ##STR3##
either alone or in combination with isomers thereof, and wherein
substituents on the cyclohexane ring are in the 1-, 2- and
4-positions, and wherein Z is a --CH.sub.2 CH.sub.2 -- group or a:
##STR4##
group, and n is an integer of 1 to 3; said method comprising
contacting 1,2,4-trivinylcyclohexane with hydrogen cyanide, in the
presence of a catalyst, said catalyst comprising an organic
phosphorous ligand and a Group VIII metal, wherein said contacting
is done at a temperature of from about -25.degree. C. to about
200.degree. C.
Also disclosed is a composition of matter comprising a cyclohexane
derivative of the formula (I-B): ##STR5##
either alone or in combination with isomers thereof, wherein the
substituents on the cyclohexane ring are in the 1-, 2- and
4-positions, Z is a --CH.sub.2 CH.sub.2 -- group or a: ##STR6##
group, and n is an integer of 1 to 3.
Another disclosure is composition of matter having the formula
XVIII, XIII, XXI or XXVI: ##STR7## ##STR8##
wherein R.sup.17 is selected from the group consisting of H,
methyl, ethyl and isopropyl, and wherein R.sup.18 and R.sup.19 are
independently H or methyl.
DETAILED DESCRIPTION OF THE INVENTION
It is one object of the present invention to provide novel
cyclohexane derivatives having nitrile groups, achieved by
hydrocyanation followed by hydrogenation to their corresponding
amines. It is another object of the present invention to provide a
method for preparing such cyclohexane derivatives. These and other
objects will become apparent in the following detailed
description.
Cyclohexane derivatives containing nitrile groups of formula (I-A):
##STR9##
either alone, as combinations of these, and/or isomers of these, in
which the substituents on the cyclohexane ring are in the 1-, 2-,
and 4-positions, Z is a --CH.sub.2 CH.sub.2 -- group or a:
##STR10##
group, and n is an integer of 1 to 3, are obtained by the
hydrocyanation of 1,2,4-trivinylcyclohexane. These compounds are
useful as precursors for monomers for the formation of polymers and
as precursors for other useful molecules. For instance, they can be
converted to corresponding amines of the formula (I-B):
##STR11##
either alone, as mixtures of these, and/or as isomers of these, in
which the substituents on the cyclohexane ring are in the 1-, 2-,
and 4-positions, Z is a --CH.sub.2 CH.sub.2 -- group or a:
##STR12##
group, and n is an integer of 1 to 3.
The inventors have discovered that 1,2,4-trivinylcyclohexane can be
contacted with hydrogen cyanide, in the presence of a catalyst and
optionally a promoter at a temperature of about -25.degree. C. to
about 200.degree. C. and optionally in the presence of a solvent,
to yield cyclohexane derivatives of the formula (I-A), wherein the
catalyst comprises a Group VIII metal, preferentially nickel, and
an organic phosphorous ligand. Further, we have discovered that
compounds or mixtures described by (I-A) may be converted to
compounds or mixtures described by (I-B) by contacting compounds or
mixtures (I-A) with hydrogen, in the presence of a transition metal
catalyst at a temperature of 50.degree. C. to 180.degree. C. and a
pressure of 50-1500 psig (340 kPa-10340 kPa), optionally in the
presence of a solvent. In addition we have discovered that mixture
(I-A) can be selectively converted to the mixtures (I-C) and/or
(I-D) by a method comprising hydrogenation of the olefin and/or the
nitrile group and mixture (I-B) can be selectively converted to
mixture (I-D) by hydrogenation of the olefin. These hydrogenations
are carried out by contacting (I-A) and/or (I-B) with hydrogen in
the presence of one or more transition metal catalysts at a
temperature of about 50.degree. C. to about 180.degree. C. and a
pressure of about 340 kPa to about 10340 kPa, optionally in the
presence of a solvent. ##STR13##
Thus, in one embodiment, the present invention provides a
hydrocyanation method for preparing cyclohexane derivatives, having
nitrile groups. Generally, the present method yields the present
cyclohexane derivatives as a mixture. The method yields several
compounds as main products, while other compounds are formed as
by-products in varying amounts. The method can be implemented to
favor one set of compounds as the main products. The set of
compounds favored in this method is a function of process
conditions and/or the type of catalyst or catalysts used and/or the
type of ligand used and/or the use of an optional promoter.
However, it is to be understood that both the individual compounds
and also the mixtures thereof are within the scope of the present
invention.
The method for making the compounds of the present invention
involves a hydrocyanation process with the use of a ligand and a
Group VIII metal or compound. Optionally, one may use a Lewis acid
in the hydrocyanation process as a promoter, and may optionally use
a solvent.
Generally, a Group VIII metal or compound thereof is combined with
at least one ligand to provide the catalyst. Among the Group VIII
metals or compounds, nickel, cobalt, and palladium compounds are
preferred to make the hydrocyanation catalysts. A nickel compound
is more preferred. A zero-valent nickel compound that contains a
ligand that can be displaced by a ligand of the prior art is the
most preferred source of Group VIII metal or Group VIII metal
compound.
Zero-valent nickel compounds can be prepared or generated according
to methods known in the art. Three preferred zero-valent nickel
compounds are Ni(COD).sub.2 (COD is 1,5-cyclooctadiene),
Ni(P(O-o-C.sub.6 H.sub.4 CH.sub.3).sub.3).sub.3 and
Ni{P(O-o-C.sub.6 H.sub.4 CH.sub.3).sub.3 }.sub.2 (C.sub.2 H.sub.4);
these are known in the art.
Alternatively, divalent nickel compounds can be combined with a
reducing agent, to serve as a source of zero-valent nickel in the
reaction. Suitable divalent nickel compounds include compounds of
the formula NiX.sup.2.sub.2 wherein X.sup.2 is halide, carboxylate,
or acetylacetonate. Suitable reducing agents include metal
borohydrides, metal aluminum hydrides, metal alkyls, Li, Na, K, Zn,
Al or H.sub.2. Elemental nickel, preferably nickel powder, when
combined with a halogenated catalyst is also a suitable source of
zero-valent nickel.
Suitable ligands for the present invention are monodentate and/or
bidentate phosphorous-containing ligands selected from the group
consisting of phosphites and phoshinites. Preferred ligands are
monodentate and/or bidentate phosphite ligands.
The preferred monodentate and/or bidentate phosphite ligands are of
the following structural formulae: ##STR14##
In formulae II, III, IV and V, R.sup.1 is phenyl, unsubstituted or
substituted with one or more C.sub.1 to C.sub.12 alkyl or C.sub.1
to C.sub.12 alkoxy groups; or naphthyl, unsubstituted or
substituted with one or more C.sub.1 to C.sub.12 alkyl or C.sub.1
to C.sub.12 alkoxy groups; and Z and Z.sup.1 are independently
selected from the group consisting of structural formulae VI, VII,
VIII, IX, and X: ##STR15##
wherein:
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and
R.sup.9 are independently selected from H, C.sub.1 to C.sub.12
alkyl, and C.sub.1 to C.sub.12 alkoxy;
W is O, S, or CH(R.sup.10); R.sup.10 is H or C.sub.1 to C.sub.12
alkyl; ##STR16##
wherein:
R.sup.11 and R.sup.12 are independently selected from H, C.sub.1 to
C.sub.12 alkyl, and C.sub.1 to C.sub.12 alkoxy; and CO.sub.2
R.sup.13,
R.sup.13 is C.sub.1 to C.sub.12 alkyl or C.sub.6 to C.sub.10 aryl,
unsubstituted or substituted. with C.sub.1 to C.sub.4 alkyl
Y is O, S, CH(R.sup.14);
R.sup.14 is H or C.sub.1 to C.sub.12 alkyl: ##STR17##
wherein
R.sup.15 is selected from H, C.sub.1 to C.sub.12 alkyl, and C.sub.1
to C.sub.12 alkoxy; and
CO.sub.2 R.sup.16,
R.sup.16 is C.sub.1 to C.sub.12 alkyl or C.sub.6 to C.sub.10 aryl,
unsubstituted or substituted with C.sub.1 to C.sub.4 alkyl
In the structural formulae II through X, the C.sub.1 to C.sub.12
alkyl, and C.sub.1 to C.sub.12 alkoxy groups may be straight chains
or branched.
Examples of bidentate phosphite ligands that are useful in the
present process include those having the formulae XI to XXXIV,
shown below wherein for each formula, R.sup.17 is selected from the
group consisting of H, methyl, ethyl or isopropyl, and R.sup.18 and
R.sup.19 are independently selected from H or methyl: ##STR18##
##STR19## ##STR20## ##STR21## ##STR22## ##STR23## ##STR24##
##STR25## ##STR26## ##STR27## ##STR28##
Suitable bidentate phosphites are of the type disclosed in U.S.
Pat. Nos. 5,512,695; 5,512,696; 5,663,369; 5688,986; 5,723,641;
5,847,191; 5,959,135; 6,120,700; 6,171,996; 6,171,997; 6,399,534;
the disclosures of which are incorporated herein by reference.
Suitable bidentate phosphinites are of the type disclosed in U.S.
Pat. Nos. 5,523,453 and 5,693,843, the disclosures of which are
incorporated herein by reference.
A preferred embodiment of this invention is the use of a bidentate
phosphite ligand of the formula XVIII, XIII, XXI, or XXVI in
combination with the Group VIII metal, preferably nickel, as
catalyst for the hydrocyanation process.
The ratio of ligand to active nickel can vary from a ligand to
nickel ratio of 0.5:1 to a ligand to nickel ratio of 100:1.
Preferentially the ligand to nickel ratio ranges from 1:1 to 4:1.
The ligands of the present invention contain trivalent phosphorus
atoms in which each trivalent phosphorous atom is known as
phosphite. The ligands useful in the present invention can be
mono-dentate ligands and/or bidentate ligands meaning that two
trivalent phosphorus atoms in the molecule are each bonded to the
same organic group, which bridges the trivalent phosphorus atoms
together. The ligands in the present invention can also be
multidentate with a number of phosphorous atoms in excess of 2 or
of polymeric nature in which the ligand/catalyst composition is not
homogeneously dissolved in the process mixture.
Optionally, the process of this invention is carried out in the
presence of one or more Lewis acid promoters that affect both the
activity and the selectivity of the catalyst system. The promoter
may be an inorganic or organometallic compound in which the cation
is selected from scandium, titanium, vanadium, chromium, manganese,
iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium,
niobium, molybdenum, cadmium, rhenium and tin. Examples include but
are not limited to ZnBr.sub.2, ZnI.sub.2, ZnCl.sub.2, ZnSO.sub.4,
CuCl.sub.2, CuCl, Cu(O.sub.3 SCF.sub.3).sub.2, CoCl.sub.2,
CoI.sub.2, FeI.sub.2, FeCl.sub.3, FeCl.sub.2, FeCl.sub.2
(THF).sub.2, TiCl.sub.4 (THF).sub.2, TiCl.sub.3, TiCl.sub.2,
ClTi(OiPr).sub.2, MnCl.sub.2, ScCl.sub.3, AlCl.sub.3, (C.sub.8
H.sub.17)AlCl.sub.2, (C.sub.8 H.sub.17).sub.2 AlCl, (iso-C.sub.4
H.sub.9).sub.2 AlCl, (C.sub.6 H.sub.5) .sub.2 AlCl, (C.sub.6
H.sub.5)AlCl.sub.2, ReCl.sub.5, ZrCl.sub.4, NbCl.sub.5, VCl.sub.3,
CrCl.sub.2, MOCl.sub.5, YCl.sub.3, CdCl.sub.2, LaCl.sub.3,
Er(O.sub.3 SCF.sub.3).sub.3, Yb(O.sub.2 CCF.sub.3).sub.3,
SmCl.sub.3, B(C.sub.6 H.sub.5).sub.3, R.sup.20 SnO.sub.3 SCF.sub.3
where R.sup.20 is an alkyl or aryl group). Preferred promoters
include CdCl.sub.2, FeCl.sub.2, ZnCl.sub.2, CoCl.sub.2, COI.sub.2,
AlCl.sub.3, B(C.sub.6 H.sub.5).sub.3, and (C.sub.6 H.sub.5).sub.3
Sn(CF.sub.3 SO.sub.3). The mole ratio of promoter to Group VIII
transition metal present in the reaction can be within the range of
about 1:16 to about 50:1, with 0.5:1 to about 2:1 being
preferred.
The ligand compositions of the present invention may be used to
form catalysts, which may be used for the hydrocyanation of
1,2,4-trivinylcyclohexane, with or without a Lewis acid
promoter.
The process comprises contacting, in the presence of the catalyst,
1,2,4-trivinylcyclohexane with a hydrogen cyanide-containing fluid
under conditions sufficient to produce a nitrile. Any fluid
containing about 1 to 100% HCN can be used. Pure hydrogen cyanide
may be used.
The hydrocyanation process can be carried out, for example, by
charging a suitable vessel, such as a reactor, with
1,2,4-trivinylcyclohexane, catalyst and optionally solvent, to form
a reaction mixture. Hydrogen cyanide can be initially combined with
other components to form the mixture. However, it is preferred that
HCN be added slowly to the mixture after other components have been
combined. Hydrogen cyanide can be delivered as a liquid or as a
vapor to the reaction. As an alternative, a cyanohydrin can be used
as the source of HCN as known in the art.
Another suitable technique is to charge the vessel with the
catalyst and the solvent (if any) to be used, and feed both the
1,2,4-trivinylcyclohexane and the HCN slowly to the reaction
mixture.
The molar ratio of 1,2,4-trivinlycyclohexane to catalyst can be
varied from about 10:1 to about 10,000:1. The molar ratio of HCN:
catalyst can be varied from 5:1 to 10,000:1. The process can be run
in continuous or batch mode.
Preferably, the reaction mixture is agitated, for example, by
stirring or shaking. The present compounds can be individually
isolated from the reaction mixture, using known conventional
methods, such as chromatography or fractional distillation.
The hydrocyanation can be carried out with or without a solvent.
The solvent, if used, can be liquid at the reaction temperature and
pressure and inert towards 1,2,4-trivinylcyclohexane and the
catalyst. Examples of suitable solvents include hydrocarbons such
as benzene, xylene, or combinations thereof; ethers such as
tetrahydrofuran (THF), nitriles such as acetonitrile, adiponitrile,
or combinations of two or more thereof. 1,2,4-trivinylcyclohexane
can itself serve as the solvent.
The exact temperature is dependent to a certain extent on the
particular catalyst being used, and the desired reaction rate.
Normally, temperatures of from -25.degree. C. to 200.degree. C. can
be used, the range of about 0.degree. C. to about 120.degree. C.
being preferred.
The process can be run at atmospheric pressure. Pressures of from
about 50.6 to 1013 kPa are preferred. Higher pressures, up to
10,000 kPa or more, can be used, if desired.
The time required can be in the range of from a few seconds to many
hours (such as 2 seconds to 72 hours), depending on the particular
conditions and method of operation.
In a first preferred embodiment, the present invention relates to
compounds with the general structure of formula (XXXVI):
##STR29##
alone or in mixtures with one another, their production, and
derivatives prepared from such compounds. For the production of the
compounds of formula XXXVI, 1,2,4-trivinylcyclohexane is reacted
with hydrogen cyanide in the presence of a group VIII catalyst,
preferably nickel, a ligand and optionally a Lewis acid promoter.
In this embodiment, a product mixture is obtained which generally
comprises cyclohexane derivatives having linear nitrites and two
olefinic groups. For example, the product obtained comprises a
mixture of formulae XXXVII, XXXVIII and XXXIX. Isomers, represented
by formula XL, XLI and XLII may be present in small amounts.
##STR30## ##STR31##
In another preferred embodiment, the present invention relates to
compounds with the general structure of formula (XLIII):
##STR32##
alone or in a mixture with one another, their production, and
derivatives prepared from such compounds. For the production of the
compounds of formula XLIII, 1,2,4-trivinylcyclohexane is reacted
with hydrogen cyanide in the presence of a Group VIII catalyst,
preferably nickel, a ligand and, optionally, a Lewis acid promoter.
In this embodiment, a product is obtained that comprises a mixture
of formulae XLIV, XLV and XLVI: ##STR33## ##STR34## ##STR35##
Isomers, represented by formulae XLVII through LV may be present in
smaller amounts.
In a third preferred embodiment, the invention relates to compounds
with the general structure of formula (LVI): ##STR36##
alone or in a mixture with one another, their production, and
derivatives prepared from such compounds wherein Z is defined as
above. For the production of the compounds of formula LVI,
1,2,4-trivinylcyclohexane is reacted with hydrogen cyanide in the
presence of a group VIII catalyst, preferentially nickel, a ligand
and, optionally a Lewis acid promoter. In this embodiment, a
product mixture is obtained that comprises LVII and to a smaller
extent compounds LVIII through LXIV: ##STR37## ##STR38##
The present cyclohexane derivatives containing nitrile groups can
be used alone or in mixtures with one another, for further
functionalization. For example, they can be converted to their
corresponding amines by hydrogenation. Thus compounds described by
(I-A) either alone or as mixtures of isomers may be contacted with
hydrogen in the presence of a catalyst, optionally in the presence
of a solvent to yield amine compounds described by (I-B).
During the hydrogenation process the feed (i.e. compounds described
by (I-A) either alone or in mixtures of isomers) is contacted with
hydrogen. The mole ratio of hydrogen to feed is not critical as
long as sufficient hydrogen is present to produce the desired
derivatives described by (I-B). Hydrogen is preferably used in
excess. Hydrogen pressures are generally in the range of about 340
kPa-10340 kPa, with about 1480 to about 7000 kPa preferred. The
hydrogenation process can be conducted at temperatures from
50.degree. C. to about 180.degree. C., preferably from 65.degree.
C. to about 100.degree. C.
Preferred catalysts for hydrogenating nitriles to amines comprise
one or more elements from the series of transition metals,
particularly useful are iron, cobalt, nickel, rhodium and
combinations thereof. The hydrogenation catalyst may also comprise
one or more elements in addition to the transition metals mentioned
above, for example, elements of Group IA (including lithium, sodium
and potassium), elements of Group IIA (including magnesium and
calcium), titanium, elements of Group VI (including chromium,
molybdenum and tungsten), elements of Group VIII (including
palladium) and/or aluminum, silicon, boron and/or phosphorous. The
hydrogenation catalyst can also be in the form of an alloy,
including a solid solution of two or more elements.
The transition metal for hydrogenation can also be supported on an
inorganic support such as alumina, magnesium oxide and combinations
thereof. The metal can be supported on an inorganic support by any
means known to one skilled in the art such as, for example,
impregnation, co-precipitation, ion exchange, or combinations of
two or more thereof. The metal can be reduced before the
hydrogenation reaction by any means known to one skilled in the art
such as, for example, pretreatment with hydrogen, formaldehyde or
hydrazine.
The hydrogenation catalyst can be present in any appropriate
physical shape or form. It can be in fluidizable forms, powders,
extrudates, tablets, spheres or combinations of two or more
thereof. The hydrogenation catalyst may be in sponge metal form,
for example, the Raney.RTM. nickels and Raney.RTM. cobalts. The
molar ratio of hydrogenation catalyst to feed (i.e. compounds
described by (I-A) either alone or in mixtures and/or isomers) can
be any ratio as long as the ratio can catalyze the hydrogenation.
The weight ratio of hydrogenation catalyst to feed is generally in
the range of from about 0.0001:1 to about 1:1, preferably about
0.001:1 to about 0.5:1. If the catalytic element is supported on an
inorganic support or is a portion of an alloy or solid solution,
the catalytic element is generally present in the range of from
about 0.1 to about 60, preferably about 1 to about 50, and most
preferably about 2 to about 50 weight percent based on the total
hydrogenation catalyst weight.
The preferred nitrile hydrogenation catalyst is a sponge metal type
catalyst. The metallic component is iron, cobalt, nickel or
combinations thereof. Commercially available catalysts of this type
are promoted or un-promoted Raney.RTM. Ni or Raney.RTM. Co
catalysts that can be obtained from the W.R. Grace and Co.
(Chattanooga, Tenn.), or alternative sponge metal catalysts
available, for example, from Activated Metals Corporation
(Sevierville, Tenn.) or Degussa (Parsippany, N.J.).
The hydrogenation can optionally be conducted in the presence of a
solvent. Suitable solvents include those known in the art as useful
for hydrogenation reactions. Examples of these are amines,
aliphatic alcohols, aromatic compounds, ethers, esters (including
lactones), and amides (including lactams). Specific examples of
solvents include: ammonia, toluene, tetrahydrofuran, methanol,
ethanol, any isomeric propanol, any isomeric butanol and water.
Preferred solvents include ammonia, toluene and methanol. It will
be appreciated that the solvent may serve to reduce the viscosity
of the system to improve fluidity of the catalyst in the reaction
vessel, as well as serve to remove the heat of reaction from the
feed and products. The solvent may be present in a range of 1% to
75% by weight of the total reaction mixture, excluding the
catalyst, preferably from 10% to 50%.
Optionally, a promoter may be used in the hydrogenation process to
alter the rate of the reaction and/or alter the selectivity of the
reaction. Suitable promoters include water, alkali or alkaline
earth metal hydroxides, quaternary ammonium hydroxides, quaternary
ammonium cyanides, quaternary ammonium fluorides, and combinations
of these. Promoters may be present at from 10 ppm to 3% by weight
of the total reaction mixture, excluding the catalyst, preferably
from 50 ppm to 1.5%.
It will be further appreciated that any olefin content of products
described by (I-A) or (I-B) (i.e. any carbon-carbon double bonds)
may be saturated using the instant hydrogenation with the further
specification that the preferred catalyst for hydrogenation of the
olefin comprises palladium, rhodium, nickel and/or ruthenium.
Hydrogenation of the olefin content can occur before, during or
after the hydrogenation of the nitrile content to amine. This
process produces compounds (I-C) and/or compounds (I-D). The
products according to the present invention can be used as monomers
for the production of polymers, or as fragrance intermediates.
Having generally described this invention, a further understanding
can be obtained by reference to certain specific examples, which
are provided herein for purpose of illustration only and are not
intended to be limiting unless otherwise specified.
EXAMPLES
Examples 1-8--Hydrocyanation
A solution of catalyst was prepared by combining Ni(COD).sub.2 in
toluene with the phosphite ligand in a ratio of Ni:ligand of 1:1.1.
This solution was sampled into a reaction vessel.
1,2,4-trivinylcyclohexane was added to the reaction vessel, the
ratio of 1,2,4-trivinylcyclohexane to catalyst was 70:1. A solution
of promoter was prepared by adding ZnCl.sub.2 to acetonitrile with
a ratio of Ni to Zn of 1:1. This solution was added to the reaction
vessel. Hydrogen cyanide was added to the reaction vessel via vapor
feed. The hydrogen cyanide reservoir was at room temperature while
the reaction vessel was maintained at 50.degree. C. The reaction
was carried out for 24 hours after which time the samples were
analyzed by standard GC methodology for products. All products were
analyzed by MS and NMR spectroscopy and compared to analytical data
obtained for isolated fractions.
Conversion Compound [%] Entry Ligand Promoter [%] (XXXVI) (XLIII)
(LVI) 1 ##STR39## ZnCl.sub.2 99.7 1.3 15.5 82.8 2 ##STR40##
ZnCl.sub.2 99.3 8.6 39.0 51.7 3 4 ##STR41## ZnCl.sub.2 none 84.7
88.7 41.8 62.0 33.1 25.2 9.9 1.5 5 ##STR42## ZnCl.sub.2 87.1 44.2
34.2 8.7 6 ##STR43## ZnCl.sub.2 87.4 41.7 35.3 10.4 7 ##STR44##
ZnCl.sub.2 76.6 47.9 24.9 3.8 8 ##STR45## ZnCl.sub.2 84.5 45.4 30.6
8.5
Example 9--Hydrocyanation
In a 500 ml flask 1,2,4-trivinylcyclohexane (100 g, 0.62 mol) was
mixed with a toluene (10 g) solution of Ni(COD).sub.2 (0.85 g, 3.1
mmol) and the following ligand (2.58 g, 3.4 mmol), XXVI with
R17=Me, R18, R19=H. ##STR46##
To this was added a solution of ZnCl.sub.2 (0.46 g, 3.4 mmol) in
acetonitrile (10 ml). A solution of hydrogen cyanide (52 g, 1.91
mol) in acetonitrile (77.6 g) was prepared and added to the above
mixture using a syringe pump. During 1 hour and 45 minutes a feed
rate of 115.6 ml/hour was maintained at 50.degree. C. Product
composition was analyzed as follows:
(XXXVI) (XLIII) (LVI) 60 minutes 13.15% 43.2% 40.4% 120 minutes
0.95% 12.66 85.23%
Example 10--Hydrocyanation
In a flask 1,2,4-trivinylcyclohexane (50 g, 0.31 mol) was mixed
with a toluene (25 g) solution of Ni(COD).sub.2 (0.42 g, 1.6 mmol)
and the following ligand (R.sup.1 O).sub.3 P, II, (4.78 g, 15.4
mmol) with R.sup.1 =--C.sub.6 H.sub.5. To this was added a solution
of ZnCl.sub.2 (0.21 g, 1.5 mmol) in acetonitrile (10 ml). A
solution of hydrogen cyanide (8.3 g, 0.31 mol) in acetonitrile
(12.5 g) was prepared and added to the above mixture using a
syringe pump. After 17 hours at 50C with a feed rate of 1.5 ml/hour
the product composition was analyzed as follows:
(XXXVI) (XLIII) (LVI) 17 hours 15.0% 0.8% --
Example 11--Hydrogenation
To a 100 cc stirred pressure reactor were added 21.18 g of (LVI), 4
g methanol, and 2 g Raney.RTM. Co 2724 slurry (Grace Davison
Catalysts, Chattanooga, Tenn.). The reactor was sealed, checked for
leaks and then charged with 30 g anhydrous ammonia. The reactor was
pressurized to 250 psig with hydrogen and heated to 75.degree. C.
at which point the pressure was increased to 900 psig with
hydrogen. The reaction proceeded 12 hours, during which time
hydrogen was replenished to the reactor as needed to maintain a
pressure of 900 psig in the reactor. Upon completion of the
reaction the mixture was filtered and distilled under vacuum to
yield 18.45 g of a colorless product. The product exhibited
infrared and nuclear magnetic resonance spectra consistent with the
absence of nitrile and the presence of amine.
Example 12--Hydrogenation
To a 100 cc stirred pressure reactor were added 22.3 g of (XLIII),
2.0 g methanol, and 2 g Raney.RTM. Co 2724 slurry. The reactor was
sealed, checked for leaks and then charged with 30 g anhydrous
ammonia. The reactor was pressurized to 250 psig with hydrogen and
heated to 75.degree. C. at which point the pressure was increased
to 900 psig with hydrogen. The reaction proceeded 6 hours, during
which time hydrogen was replenished to the reactor as needed to
maintain a pressure of 900 psig in the reactor. Upon completion of
the reaction the mixture was filtered and the solvent removed by
evaporation. The product exhibited infrared (IR) and nuclear
magnetic resonance (NMR) spectra consistent with the absence of
nitrile and the presence of amine and olefin, i.e. olefin remained
in the molecule and available for further functionalization or
hydrogenation. The product was next added to a 100 cc stirred
pressure reactor along with 2 g of 5% Pd/carbon catalyst, and 30 g
of tetrahydrofuran and heated at 75.degree. C. with hydrogen at 500
psig pressure for 4 hours. Since the product NMR suggested that
olefin content still remained in the product it was submitted to
additional hydrogenation with 5% Pd/carbon catalyst. The final
product mixture was filtered and distilled under vacuum to yield
14.51 g of a colorless product with NMR and IR spectra consistent
with the absence of nitrile and olefin but the presence of
amine.
* * * * *